Absorption and fluorescence lineshape theory for polynomial potentials

Andre Anda; Luca De Vico; Thorsten Hansen; Darius Abramavičius

doi:10.1021/acs.jctc.6b00997

Absorption and fluorescence lineshape theory for polynomial potentials

Andre Anda^*, Luca De Vico, Thorsten Hansen, Darius Abramavičius

^*Corresponding author for this work

Department of Chemistry

17 Citations (Scopus)

Abstract

The modeling of vibrations in optical spectra relies heavily on the simplifications brought about by using harmonic oscillators. However, realistic molecular systems can deviate substantially from this description. We develop two methods which show that the extension to arbitrarily shaped potential energy surfaces is not only straightforward, but also efficient. These methods are applied to an electronic two-level system with potential energy surfaces of polynomial form and used to study anharmonic features such as the zero-phonon line shape and mirror-symmetry breaking between absorption and fluorescence spectra. The first method, which constructs vibrational wave functions as linear combinations of the harmonic oscillator wave functions, is shown to be extremely robust and can handle large anharmonicities. The second method uses the cumulant expansion, which is readily solved, even at high orders, thanks to an ideally suited matrix theorem.

Original language	English
Journal	Journal of Chemical Theory and Computation
Volume	12
Issue number	12
Pages (from-to)	5979-5989
Number of pages	11
ISSN	1549-9618
DOIs	https://doi.org/10.1021/acs.jctc.6b00997
Publication status	Published - 2016

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title = "Absorption and fluorescence lineshape theory for polynomial potentials",

abstract = "The modeling of vibrations in optical spectra relies heavily on the simplifications brought about by using harmonic oscillators. However, realistic molecular systems can deviate substantially from this description. We develop two methods which show that the extension to arbitrarily shaped potential energy surfaces is not only straightforward, but also efficient. These methods are applied to an electronic two-level system with potential energy surfaces of polynomial form and used to study anharmonic features such as the zero-phonon line shape and mirror-symmetry breaking between absorption and fluorescence spectra. The first method, which constructs vibrational wave functions as linear combinations of the harmonic oscillator wave functions, is shown to be extremely robust and can handle large anharmonicities. The second method uses the cumulant expansion, which is readily solved, even at high orders, thanks to an ideally suited matrix theorem.",

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T1 - Absorption and fluorescence lineshape theory for polynomial potentials

AU - Anda, Andre

AU - De Vico, Luca

AU - Hansen, Thorsten

AU - Abramavičius, Darius

PY - 2016

Y1 - 2016

N2 - The modeling of vibrations in optical spectra relies heavily on the simplifications brought about by using harmonic oscillators. However, realistic molecular systems can deviate substantially from this description. We develop two methods which show that the extension to arbitrarily shaped potential energy surfaces is not only straightforward, but also efficient. These methods are applied to an electronic two-level system with potential energy surfaces of polynomial form and used to study anharmonic features such as the zero-phonon line shape and mirror-symmetry breaking between absorption and fluorescence spectra. The first method, which constructs vibrational wave functions as linear combinations of the harmonic oscillator wave functions, is shown to be extremely robust and can handle large anharmonicities. The second method uses the cumulant expansion, which is readily solved, even at high orders, thanks to an ideally suited matrix theorem.

AB - The modeling of vibrations in optical spectra relies heavily on the simplifications brought about by using harmonic oscillators. However, realistic molecular systems can deviate substantially from this description. We develop two methods which show that the extension to arbitrarily shaped potential energy surfaces is not only straightforward, but also efficient. These methods are applied to an electronic two-level system with potential energy surfaces of polynomial form and used to study anharmonic features such as the zero-phonon line shape and mirror-symmetry breaking between absorption and fluorescence spectra. The first method, which constructs vibrational wave functions as linear combinations of the harmonic oscillator wave functions, is shown to be extremely robust and can handle large anharmonicities. The second method uses the cumulant expansion, which is readily solved, even at high orders, thanks to an ideally suited matrix theorem.

U2 - 10.1021/acs.jctc.6b00997

DO - 10.1021/acs.jctc.6b00997

M3 - Journal article

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AN - SCOPUS:85005987384

SN - 1549-9618

VL - 12

SP - 5979

EP - 5989

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

IS - 12

ER -

Absorption and fluorescence lineshape theory for polynomial potentials

Abstract

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